Nickel zinc electrochemical cell incorporating dendrite blocking ionically conductive separator

Abstract

A nickel-zinc electrochemical cell is disclosed using a polymer matrix separator. The polymer matrix separator includes a polymerization product of one or more monomers selected from the group of water-soluble, ethylenically-unsaturated acids and acid derivatives, and a crosslinking agent, and serves as a primary or supplemental source of electrolyte ionic species for the electrochemistry. Ionic species is contained as a solution phase within the polymer matrix membrane, allowing it to behave as a liquid electrolyte without the disadvantages. In secondary batteries (i.e., rechargeable), polymer matrix membranes are particularly useful as both an electrolyte reservoir and as a dendrite resistant separator between the charging electrode and the zinc electrode. The polymer matrix membrane protects the electrodes from corrosion and prevents zinc oxidation product from the zinc electrode to contaminate the electrolyte.

1 . A nickel-zinc battery comprising a zinc based electrode, a nickel based electrode, and polymer matrix membrane having a crosslinked structure, the polymer matrix membrane comprising 
 a polymerization product of one or more monomers selected from the group of water-soluble, ethylenically-unsaturated acids and acid derivatives; and    a crosslinking agent,    wherein aqueous electrolyte is supported within a volume within the polymer matrix membrane created by the crosslinked structure.    
     
     
         2 . The nickel-zinc battery as in  claim 1 , wherein the polymer matrix membrane further comprises a water-soluble or water-swellable polymer.  
     
     
         3 . The nickel-zinc battery as in  claim 1 , wherein the polymer matrix membrane further comprises a chemical polymerization initiator.  
     
     
         4 . The nickel-zinc battery as in  claim 1 , wherein the polymer matrix membrane further comprises a water-soluble or water-swellable polymer; and a chemical polymerization initiator.  
     
     
         5 . The nickel-zinc battery as in  claim 1 , wherein the water soluble ethylenically unsaturated acids and acid derivatives of the polymer matrix membrane have the general formula:  
       
         
           
           
               
               
           
         
       
       wherein R1, R2, and R3 are independently selected from the group consisting of H, C, C2-C6 alkanes, C2-C6 alkenes, C2-C6 alkynes, aromatics, halogens, carboxylic acid derivatives, sulfates and nitrates; and 
 R4 is selected from the group consisting of NR5, NHR5, NH2, OH, H, halides, OR5, and carboxylic acid derivatives, wherein R5 is selected from the group consisting of H, C, C2-C6 alkanes, C2-C6 alkenes, C2-C6 alkynes, and aromatics.  
 
     
     
         6 . The nickel-zinc battery as in  claim 1 , wherein the water soluble ethylenically unsaturated acids and acid derivatives of the polymer matrix membrane are selected from the group consisting of methylenebisacrylamide, acrylamide, methacrylic acid, acrylic acid, fumaramide, fumaric acid, N-isopropylacrylamide, N, N-dimethylacrylamide, 3,3-dimethylacrylic acid, maleic anhydride, and combinations comprising at least one of the foregoing ethylenically unsaturated acids and derivatives.  
     
     
         7 . The nickel-zinc battery as in  claim 1 , wherein the water soluble ethylenically unsaturated acids and acid derivatives of the polymer matrix membrane are selected from the group consisting of 1-vinyl-2-pyrrolidinone, the sodium salt of vinylsulfonic acid, and combinations comprising at least one of the foregoing ethylenically unsaturated acids and derivatives.  
     
     
         8 . The nickel-zinc battery as in  claim 1 , wherein the ethylenically unsaturated acids or acid derivatives of the polymer matrix membrane comprises about 5% to about 50%, by weight, of the total monomer solution prior to polymerization.  
     
     
         9 . The nickel-zinc battery as in  claim 1 , wherein the ethylenically unsaturated acids or acid derivatives of the polymer matrix membrane comprises about 7% to about 25%, by weight, of the total monomer solution prior to polymerization.  
     
     
         10 . The nickel-zinc battery as in  claim 1 , wherein the ethylenically unsaturated acids or acid derivatives of the polymer matrix membrane comprises about 10% to about 20%, by weight, of the total monomer solution prior to polymerization.  
     
     
         11 . The nickel-zinc battery as in  claim 1 , wherein the crosslinking agent of the polymer matrix membrane is of the general formula:  
       
         
           
           
               
               
           
         
       
       wherein i=1→n, and n≧2; 
 R2,i, R3,i, and R4,i are independently selected from the group consisting of H, C, C2-C6 alkanes, C2-C6 alkenes, C2-C6 alkynes, aromatics, halogens, carboxylic acid derivatives, sulfates and nitrates;  
 R1 is selected from the group consisting of N, NR5, NH, O, and carboxylic-acid derivatives, wherein R5 is selected from the group consisting of H, C, C2-C6 alkanes, C2-C6 alkenes, C2-C6 alkynes, and aromatics.  
 
     
     
         12 . The nickel-zinc battery as in  claim 1 , wherein the crosslinking agent of the polymer matrix membrane is selected from the group consisting of methylenebisacrylamide, ethylenebisacrylamide, any water-soluble N,N′-alkylidene-bis(ethylenically unsaturated amide), 1,3,5-Triacryloylhexahydro-1,3,5-triazine, and combinations comprising at least one of the foregoing crosslinking agents.  
     
     
         13 . The nickel-zinc battery as in  claim 1 , wherein the crosslinking agent of the polymer matrix membrane comprises about 0.01% to about 15%, by weight, of the total monomer solution prior to polymerization.  
     
     
         14 . The nickel-zinc battery as in  claim 1 , wherein the crosslinking agent of the polymer matrix membrane comprises about 0.5% to about 5%, by weight, of the total monomer solution prior to polymerization.  
     
     
         15 . The nickel-zinc battery as in  claim 1 , wherein the crosslinking agent of the polymer matrix membrane comprises about 1% to about 3%, by weight, of the total monomer solution prior to polymerization.  
     
     
         16 . The polymer matrix material as in  claim 1 , wherein the electrolyte comprises KOH.  
     
     
         17 . The nickel-zinc battery as in  claim 2 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane is selected from the group consisting of polysulfone (anionic), poly(sodium-4-styrenesulfonate), carboxymethyl cellulose, polysulfone (anionic), sodium salt of poly(styrenesulfonic acid-co-maleic acid), corn starch, any other water-soluble or water-swellable polymers, and combinations comprising at least one of the foregoing polymers.  
     
     
         18 . The nickel-zinc battery as in  claim 2 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane comprises less than about 30%, by weight, of the polymer matrix material.  
     
     
         19 . The nickel-zinc battery as in  claim 2 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane comprises about 1% to about 10%, by weight, of the polymer matrix material.  
     
     
         20 . The nickel-zinc battery as in  claim 2 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane comprises about 1% to about 4%, by weight, of the polymer matrix material.  
     
     
         21 . The nickel-zinc battery as in  claim 4 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane is selected from the group consisting of polysulfone (anionic), poly(sodium-4-styrenesulfonate), carboxymethyl cellulose, polysulfone (anionic), sodium salt of poly(styrenesulfonic acid-co-maleic acid), corn starch, any other water-soluble or water-swellable polymers, and combinations comprising at least one of the foregoing polymers.  
     
     
         22 . The nickel-zinc battery as in  claim 4 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane comprises less than about 30%, by weight, of the polymer matrix material.  
     
     
         23 . The nickel-zinc battery as in  claim 4 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane comprises about 1% to about 10%, by weight, of the polymer matrix material.  
     
     
         24 . The nickel-zinc battery as in  claim 4 , wherein the water-soluble or water-swellable polymer of the polymer matrix membrane comprises about 1% to about 4%, by weight, of the polymer matrix material.  
     
     
         25 . The nickel-zinc battery as in  claim 3 , wherein the chemical polymerization initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfates and peroxides, and combinations comprising at least one of the foregoing initiators.  
     
     
         26 . The nickel-zinc battery as in  claim 3 , wherein the chemical polymerization initiator comprises less than about 3%, by weight, of the polymer matrix material.  
     
     
         27 . The nickel-zinc battery as in  claim 4 , wherein the chemical polymerization initiator is selected from the group consisting of ammonium persulfate, alkali metal persulfates and peroxides, and combinations comprising at least one of the foregoing initiators.  
     
     
         28 . The nickel-zinc battery as in  claim 4 , wherein the chemical polymerization initiator comprises less than about 3%, by weight, of the polymer matrix material.